Diamino-s-triazines

ABSTRACT

The disclosure covers diamino-s-triazines which are useful in polymer synthesis, such as polyimides. Also covered are dinitros-triazines which can be used as intermediates for the diamino compounds. The diamines are prepared by a condensation of 2substituted-4,6-dichlorotriazines with diamines or with nitroamines. The product from the latter reaction can be reduced subsequently to diamines.

United States Patent Winter et al.

[4 1 Aug. 28, 1973 DlAMINO-S-TRIAZINES Inventors: Roland Winter, Armonk;Raymond Seltzer, New York, both of NY.

Assignee: Ciba-Geigy Corporation,

Greenburgh, N.Y.

Filed: July 15, 1970 Appl. No.: 55,240

U.S. Cl 260/249.6, 260/2498, 260/2499, 260/78 R, 260/830 R Int. Cl C07d55/20 Field of Search 260/2498, 249.9, 260/2496 References Cited UNITEDSTATES PATENTS 2/1971 Feichtinger et a] 260/2499 1/1972 D'Alelio260/2496 3,3l0,557 3/1967 Kleemann 260/2498 X OTHER PUBLICATIONSTheilheimer, Synthetic Methods of Organic Chemistry," Vol. 12, Pub., S.Karger, New York 1958), p. 21.

Primary Examiner-John M. Ford Attorney-Karl F. Jorda, Nestor W. Shustand Bruce M. Collins 5 7] ABSTRACT 19 Claims, No DrawingsDIAMINO-S-TRIAZINES DETAILED DISCLOSURE The diamino-s-triazines of thisinvention are represented by the general formula wherein R is alkylene,cycloalkylene, arylene, alkarylene, aralkylene, or diarylene ether,diarylene thioether, diarylene methane or diarylene sulfone group and aheterocyclic group.

R is hydrogen, alkyl, cycloalkyl, amino, arylamino, alkyl amino,pyrrolidino, piperidino, phenyl, halo, hydroxyl or carboxyl group.

These amino-s-triazine compounds can be used generally for the sameapplications as other organic diamines. For example, they can be used inmaking various polymers, such a polyimides, polyamides and polyureas.They are also useful in other areas, as dyestuff intermediates or ashardeners for epoxy resins.

The (lower) alkyl group employed herein means a straight, or branchedchain alkyl group having up to four carbon atoms. Examples of suchgroups are methyl, ethyl, propyl, isopropyl, butyl and the like.

The alkyl groups mentioned above in reference to R and R have up toeight carbon atoms, that is, methyl, ethyl, propyl, isopropyl, butyl,tert-butyl, hexyl, octyl and its isomers. Cycloalkyl groups have fromthree to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The aryl, alkaryl and aralkyl groups have up to about 14carbon atoms, such as phenyl, biphenyl, tolyl, naphthyl, anthracyl,ethylnaphthyl, benzyl, l-phenylhexyl, l-phenylethyl, 3 ,5- diethylphenyland the like. The heterocyclic group in R can be derived from a furan, athiophene or a pyridine.

The R group in the above general structure is more specifically selectedfrom the following groups:

a. ortho, meta and para phenylene, biphenylene,

naphthyl, anthracyl I drogen, phenyl, substituted phenyl or an aminogroup illustrated below:

-NH lower dialkylamino groups such as, dimethylamino, diethylamino,dipropylamine, diiso- 5 triazine compounds of this invention.

2-Phenyl-4,6-bis(4-aminoanilino)-s-triazine 2-PhenyI-4,6-bis( 3-aminoanilino )-s-triazine 2-Anilino-4,6-bis(4-aminoanilino)s-triazine2-N-Methylanilino-4,6-bis( 3 '-aminoanilino )-striazine2-DimethyIamino-4,6-bis( 3 -aminoanilino )-s-triazine2-Dibutylamino-4,6-bis(3-aminopropylamino)-striazine2-Diphenylamino-4,6-bis( 2 '-aminoanilino )-s-triazine2-Diphenylamino-4,6-bis(3'-aminoanilino)-s-triazine2-Diphenylamino-4,6-bis(4'-aminoanilino )-s-triazine2-Methyl-4,6-bis(8'-aminooctylamino)-s-triazine2-n-Octyl4,6-bis(4'-aminobutylamino)-s-triazine2-Isopropyl-4,6-bis(4-aminobutylamino )-s-triazine2-Phenyl-4,6-bis(2=methyl-4-aminoanilino)-striazine2-Diphenylamino-4,6-bis(3'-aminocyclohexylamino)-s-triazine2-Phenyl-4,6-bis(aminocyclopropylamino)-s-triazine 2-Phenyl-4,6-bis( 3-aminopyridinylamino-5 striazine 2-Piperidino-4,6-bis( 3 '-aminoanilino)-s-triazine 2,4-Bis( 3 '-aminoanilino )-s-triazine2-Cyclohexyl-4,6-bis(3'-aminoanilino)-s-triazine 2-Amino-4,6-bis( 3'aminoanilino )-s-triazine2-Diphenylarnino-4,6-bis[4'-(4"-aminophenoxyanilino)]-s-triazine2-Diphenylamino-4,6-bis[4'-(4"-aminobenzyl- )anilino]-s-triazine2,4-(3'-Aminoanilino)-s-triazine The amino-s-triazine compounds of thisinvention can be prepared by various methods. One method comprisesreacting a 2-aryl, alkyl, or amino substituted-4,6- dichloro-s-triazinewith a large excess of a diamine. The reaction is generally conducted insolvents selected from tetrahydrofuran, acetone, methylethyl ketone,methyl-ethyl ketone-water, dioxane and dimethylformamide between 50C C.It may be advantageous to conduct the reaction in the presence of acidacceptors such as sodium carbonate or sodium hydroxide. In reactionsincluding 2-diphenyla.mino-4,6-dichloro-striazine and meta or paraphenylenediamine, it is especially advantageous to conduct the reactionin dioxane. The product is obtained as a dioxane complex which can bereadily isolated and purified.

Another method for preparing these compounds comprises reacting 1 moleof 2-substituted-4,6- dichloro-s-triazine with 2 moles of a nitroaminocompound. The resulting intermediate dinitro compound is reduced to thedesired diamino-striazine with a stan dard reducing agent such asstannous chloride and hyaqueous hydrochloric acid) or catalytically(hydrogen with a palladium or charcoal catalyst) to give the desired2,4-bis-diamino compound.

In the above described one-step reaction where a diamino compound isreacted with a dichloro triazine, an

undesirable side reaction between the diamine and two 1 differenttriazine molecules is likely to occur. To minimize the formation ofundesirable products which contain more than one triazine nucleus, it isadvantageous to use an excess of the diamine, to carry out thecondensation reaction at elevated temperatures, preferably between 50Cand 100C or higher, depending on the reactants and the solvent employedand to add the dichloro-s-triazine slowly to the diamine.

When the above precautions are observed, the reation will favor theformation of the desired products over the undesired ones.

A further embodiment of the invention are the dinitro-s-triazinecompounds which are prepared by one of the above mentioned methods andwhich are intermewherein R is a divalent aromatic group exemplifiedabove and R is as defined above in connection with the diaminocompounds.

Illustrative examples of the dinitro-s-triazine compounds are listedbelow:

2-Phenyl-4,6-bis(4'-nitroanilino)-s-triazine 2-Phenyl-4,6-bis( 3'-nitroanilino)-s-triazine 2-Anilin0-4,6-bis(4-nitroanilino)-s-triazine2-N-Metylanilino-4,6-bis( 3 '-nitroanilino )-s-triazine2-Dimethylamino4,6-bis( 3 '-nitroanilino)-s-triazine2-Diphenylamino-4,6-bis(3-nitroanilino)-s-triazhie2-lsopropyl-4,6-bis(4'-nitrobenzyl)-s-triazine2-Phenyl-4,6-bis(2'-methyl-4'-nitroanilino)-striazine 2-Piperidino-4,6-bis( 3 '-nitroanilino )-s-triazine 2 ,4-Bis( 3 '-nitroanilino)-s-triazine 2-Cyclohexyl-4,6-bis( 3 '-nitroanilino )-s-triazine2-Amino-4,6-bis(3'-nitroanilino)-s-triazine2-Diphenylamino-4,6-bis[4'(4"-nitrophenoxy)anilino]-s-triazine2-Diphenylamino-4,6-bis[4'-(4"-nitrobenzyl- )anilinol-s-triazine2,4(m-nitroanilino)-s-triazine 2-Hydroxy-4,6-bis( 3 '-nitroanilino)-s-triazine 2-Carboxy-4,5-bis(3-nitroanilino)-s-triazine2-Chloro-4,6-bis( 3 -nitroanilino )-s-triazine The above describedmethods of preparing the dinitro-s-triazines and the diamino-s-triazinesof this invention are further illustrated in the examples below.

EXAMPLE 1 2-Diphenylamino-4,6-Bis-( 3 '-Aminoanilino )-s- TriazineDioxane Complex To a solution of 432.0g(4.0 mole) of mphenylenediaminein 600 ml. of dioxane was added 84.- 8g(0.80 mole) of sodium carbonate.This mixture was heated to reflux, and while stirring in a nitrogenatmosphere, a solution of 126.8g(0.40 mole) of 2- 5diphenylamino-4,6-dichloro-s-triazine in 800 ml of dioxane was addeddropwise over a 5.75 hour period. After the addition was complete, thereaction was stirred and refluxed overnight. After cooling, the reactionmixture was poured into 2 liters of ice water with stirring. The.resulting solid was filtered, washed chloride free with water and thendried to give l8l.0g of material. This crude product was stirred andrefluxed in 1800 ml. of acetone for 30 minutes and filtered. The residuewas discarded.

The acetone was stripped from the filtrate to give 158.7g of solid, mp.107-30. This material was added to 800 ml. of benzene and brought toboiling; 350 ml. of dioxane was added to obtain solution followed by 20gof charcoal. The mixture was filtered and upon cooling 102.79g(5lpercent) of the product having the m.p. of l38l42C was obtained. Theyield and the analysis is based on the dioxane complex.

Calculated for c .H N,o,: C, 67.86; H, 5.88; N, 20.42 Found: C, 67.67;H, 5.93; N, 20.32.

EXAMPLE 2 2-Diphenylamino-4,6-Bis( 3 '-Aminoanilino )-s-Triazine To asolution of l08.0g( l .0mole) of mphenylenediamine in 250ml of water wasadded a few drops of a phenolphthalein solution. While stirring thissolution at reflux, solutions of 3l.7g(0.l0 mole) of 2-diphenylamino-4,6-dichloro-s-triazine in 300 ml of methyl ethyl ketoneand 8.0g(0.20 mole) of sodium hydroxide in 72ml of water were addeddropwise and simultaneously at such a rate as to keep the pH below 8.After the addition was complete, the reaction mixture was refluxed for 2hours, the methyl ethyl ketone, was then removed by distillation. Thereaction mixture was cooled and filtered. The residue was washed withwater until chloride free and dried to give 48.4g of the crude product.

The crude was heated in 450ml of boiling acetone and filtered, and thefiltrate stripped to dryness leaving 393g of solid. This material wasrecrystallized from hot isopropanol yielding 20.7g of2-diphenylamino-4,6- bis(3'-aminoanilino)s-triazine having a mp. ofl88l9 1C.

Calculated for C l-l bi C, 70.41; H, 5.25; N, 24.33 Found: C, 70.08; H,5.l l; H, 24.45

EXAMPLE 3 2-Dimethylamino4,6-Bis-(3'Aminoanilino)-s-Triazine To asolution of 540.5g(5.0 moles) of mphenylenediamine in 2,500ml of waterand ml of methyl ethyl ketone, at reflux and uneer nitrogen, was

added dropwise a solution of 96.5g (0.50 mole) of 2-dimethylamino-4,6-dichloro-s-triazine in 500ml of methyl ethyl ketone.During this addition the pH was maintained between 8 and by thesimultaneous addition of 50 percent aqueous sodium hydroxide solution.After the additions were complete, the reaction mixture was stirred atreflux for 5 hours, and then the methyl ethyl ketone was distilled offat a reduced pressure. The reaction mixture was filtered and the residuewashed with methanol and then twice thoroughly saturated with 1,000m1 ofmethanol in an electric blender and filtered. The residue was washedwith methanol and dried to give 127.0(76 percent) of the product, m.p.197199" C. Recrystallization from ethanol gave a m.p. of l97200C.Calculated for C H N C, 60.69; H, 5.99; N, 33.31

Found: C, 60.80; H, 6.04; N, 33.25.

EXAMPLE 4 2,4-Bis-(3-Aminoanilino)-sTriazine To a solution of15.48g(0.04mole) of 2-chloro-4,6- bis(-m-nitroanilino-s-triazine,prepared from cyanuric and m-nitroaniline, in 200ml of tetrahydrofuranwas added 4.04g(0.04mole) of triethylamine and 10g of 5 percentpalladium on charcoal. The mixture was placed in Parr shaker at 50 psipressure, and shaken overnight at room temperature. The reaction wasthen filtered and the residue washed with 400ml of tetrahydrofuran andwith water until chloride free. The residue was then washed withdimethylformamide (DMF) until the filtrate was colorless. The DMFsolution was then added to one liter of water. The resulting solid wasfiltered, washed with water and then stirred in 200 ml. of boilingacetone for minutes. The product was filtered and dried under vacuum at50. The yield of 2,4-bis-(3- aminoani1ino)-s-triazine was 8.20(70percent) m.p. 2697l. Calculated for C, H -,N,: C, 61.40; H, 5.16; N,33.44

Found: C, 61.16; H, 5.17; N, 33.24

EXAMPLE 5 triturated with water and filtered. On standing 18.8g of solidcrystallized from the filtrate. This material was recrystallized fromisopropanol yielding 10.40g.(34 percent) of2-amino-4,6-bis-(3-aminoanilino)-s-triazine having a m.p. of 198-200C.Calculated for C H N z C, 58.44; H, 5.19; N, 36.36

Found: C, 58.72; H, 5.35; N, 36.30

EXAMPLE 6 2-Phenyl-4,6-Bis( 3 'Aminoani1ino)-s-Triazine To a solution of86.0g(0.80mole) of mphenylenediamine in 300ml of dioxane was added25.0g(0.23mole) of sodium carbonate. The mixture was heated to reflux,and a solution of 18.0(0.08mole) of 2-phenyl-4,6-dichloro-s-triazine in250ml of dioxane was added dropwise. After the addition was complete,the reaction mixture was refluxed for 15 hours, cooled and then pouredinto 3 liters of ice-water. The mixture was filtered, and the residuewas washed free of chloride with water and dried.

Yield-300g.

The crude was recrystallized from isopropanol to yield l6.5g(56 percent)of 2-phenyl-4,6-bis(3- aminoanilino)-s-triazine which decomposed at178C. Calculated for C ,H ,N C, 68.29; H, 5.18; N, 26.55

Found: C, 68.24; N, 5.38; N, 26.27

EXAMPLE 7 2-Diphenylamino-4,6-Bis[4'(4"-Aminophenoxy)ani1ino]-s-TriazineTo a solution of 60.0g(0.30 mole) of bis(-paminophenyl) ether in 250mlof diglyme at C was added dropwise a solution of 15.0g(0.047mole) of 2-diphenylamino-4,6-dichloro-s-triazine. After the addition was complete,the reaction was heated at 100 for 24 hours, cooled and then added toice-water. The mixture was filtered, washed free of chloride ion withwater and dried to give 29.0g(96 percent) of product, m.p. 250C. Washingthe crude with 2-propanol or a recrystallization from dioxanewater didnot raise the melting point. Calculated for C E-1 N 0 C, 72.65; H, 5.00;N, 17.37

Found: C, 72.76; H, 4.97; N, 1767.

EXAMPLE 8 2-Diphenylamino-4,6-Bis[4-(4"-Aminobenzyl-)anilino]-s-Triazine A solution of 100g. (0.5mole) of4,4'-methylenediamine in 1,000ml of dioxane was heated at reflux, andover a 3 hour period, a solution of 31.7g(0.1mole) of2-diphenyl-amino-4,-dichloro-s-triazine in 250ml of dioxane was addeddropwise thereto. After additional refluxing for 3 hours, the mixturewas filtered hot; the filtrate was concentrated to a volume of 600ml.and diluted with 2000ml of isopropanol. After crystallization overnightin the refrigerator, the product was filtered and oven dried; yield40.6g. (63 percent). Recrystallization from n-butanol yielded 16.5g ofthe diamine as an off white powder, m.p. 242-8c. Calculated for Found:C. 76.19; H. 5.74; N. 17.18;

C, 76.31; H, 5.82; N, 17.31

EXAMPLE 9 2-Diphenylamino-4,6-Bis(4-Aminoanilino)-s-triazine A mixtureof 317g(1 mole) of 2-diphenylamino-4,6- dichloro-s-triazine,276g(2moles) of p-nitroaniline and 3,000ml of anisole was heated atreflux for 16 hours under a nitrogen atmosphere. During this periodhydrogen chloride was evolved. The reaction mixture was cooled, and theprecipitate isolated by filtration. The filter cake was washedsuccessively with methanol, aqueous ammonia, water and again withmethanol, then dried at 100C at a deduced pressure, yielding 474(91percent Yield) 2-dipheny1amino-4,6-bis(4'- nitroanilino)-s-triazine m.p.3346C as an off-white solid.

Calculated for 27Hz0NsO Z C. 62.30; H, 3.87; N, 21.53

Found: C, 61.92; H, 3.86; N, 21.47;

C, 61.91; H, 3.70; N, 21.49

The dinitro-intermediate above was reduced to the diamine as follows:mixture of 208g(0.4mole) of 2-diphenyl-amino-4,6-bis(p-nitroanilino)-s-triazine, 223(4g-atoms) of ironpowder and 2,000ml of dioxane was heated to reflux. Then a pasteprepared from 10g of iron powder and hydrochloric acid was added as anactivator. Over the course of 45 minutes, 40ml of water was addeddropwise to the refluxing reaction mixture. After refluxing foradditional 4 hours, the suspension was diluted with 1,000ml of dioxaneand 1,000ml of dimethylformamide, heated with charcoal and then cooledin an icebath. The crystalline off-white precipitate was filtered anddried at 50 overnight at 0.1mm Hg yielding 125g (68 percent) of2-diphenylamino-4,6- bis(4'-aminoanilino)-s-triazine m.p. 2384 Thisproduct contains 3/4 mole of solva te-dioxane. Calculated for CZ'IHZJNBX 3/4 dioxane: C, 68.42; H, 5.74; N,

21.28 Found: C, 68.60; H, 5.94; N. 21.74;

C, 68.54; H, 6.03; N. 21.73

Dioxane is retained on further drying at 105C, 0.1mm Hg.

EXAMPLE 10 2-Diphenylamino-4,6-bis(2'-Aminoanilino )-s-Triazine Inanalogy to the procedure above, o-nitroaniline was converted into2-diphenylamino-4,6-bis( 2 nitroanilino-s-triazine. Afterrecrystallization from ethyl acetate the product was isolated in 78percent yield, m.p. 242-243.5C. Calculated for C H N O C; 62.30 H; 3.87N; 21.53

Found: C; 62.15 H; 3.66 N; 21.65. Reduction of the dinitro compound(104g, 0.2moles) with iron powder (112g, Zg-atoms) in 500ml of boilingdioxane was carried out by activating with 2 ml of a mixture of ironpowder and hydrochloric acid followed by gradual addition of 25ml ofwater and reflux for 5 hours. To isolate the product the dioxanesolution was concentrated and diluted with heptane. Recrystallizationfrom a mixture of 500ml of acetone and 500ml of water yielded 64.9g (71percent) of white 2- diphenylamino-4,6-bis(2'-aminoanilino)-s-triazine;m.p. 243244C. Calculated for Found: C; 70.39 H; 5.23 N; 23.98 Anothersample of the dinitro compound was hydrogenated in dioxane solution atroom temperature at SOps; over percent palladium on charcoal, whichproduced the above diamine in 90 percent yield.

What is claimed is:

l. A diamino compound having the formula wherein R is alkylene of up toeight carbon atoms, cycloalkylene from three to six carbon atoms,arylene, alkarylene, aralkylene, or diarylene ether, diarylenethioether, diarylene methane or diarylene sulfone, said arylene,alkarylene and aralkylene groups having up to 14 carbon atoms, and saidarylene alone or in a combined form being a carbocyclic group, and

R is hydrogen, alkyl of up to eight carbon atoms, cy-

cloalkyl from three to six carbon atoms, phenyl, amino group N-(loweralkyl)amino, (lower) dialkylamino, anilino, diphenylamino,naphthylanilino, pyrrolidino, piperidino, halogen, carboxyl or hydroxylgroup.

2. A diamino of claim 1, wherein R is a. ortho, meta, or para phenylene,biphenylene,

naphthylene or anthracylene,

b. the group where X is sulfur, oxygen, sulfone or methylene, or

c. cyclopentylene cyclopentyl or cyclohexylene group.

3. The diamine of claim 1 where R is phenylene.

4. The diamine of claim 1 where R is phenyl group.

5. The diamine of claim 1 where R is anilino group.

6. The diamine of claim 1 where R is diphenylamino group.

7. The diamine of claim 1 where R is p,pdiphenylene ether and R isphenyl.

8. The diamine of claim 1, which is'2-diphenylamino-4,6-bis(3'-aminoanilino)-s-triazine 9. The diamine of claim 1, which is2-diphenylarnino- 4,6-bis(4'-aminoanilino)-s-triazine.

10. The diamine of claim 1, which is 2- diphenylamino-4,6-bis( 2'-arninoanilino )s-triazine.

11. The diamine of claim 1, which is 2,4-bis(3-aminoanilino)-s-triazine.

12. The diamine of claim 1, which is dimethylamino-4,6-bis( 3'-aminoanilino )-s-triazine.

13. The diamine of claim 1, which is 2-amino-4,6- bis( 3'-aminoanilino)-s-triazine.

14. The diamine of claim 1, which is 2-phenyl-4,6-bis(3-aminoanilino)-s-triazine.

15. The diamine of claim 1, which is 2-diphenylamino-4,6-bis[4'-(4"-arninophenoxy)anilino}-s-triazine.

16. The diamine of claim I, which is 2-diphenylamino-4,6-bis{4'-(4"-aminobenzyl)anilino]-striazine.

17. A diamine-dioxane complex wherein said diamine has the formulawherein amino group N-(lower alkyl)amino, (lower)dialkylamino, anilino,diphenylamino, naphthylanilino, pyrrolidino, piperidino, halogen,carboxyl or hydroxyl group. 18. The complex of claim 16 wherein theratio of the diamine to dioxane is 1:1.

19. The complex of claim 16 wherein the ratio of the diamine to dioxaneis 1:0.75.

2. A diamino of claim 1, wherein R'' is a. ortho, meta, or paraphenylene, biphenylene, naphthylene or anthracylene, b. the group
 3. Thediamine of claim 1 where R'' is phenylene.
 4. The diamine of claim 1where R2 is phenyl group.
 5. The diamine of claim 1 where R2 is anilinogroup.
 6. The diamine of claim 1 where R2 is diphenylamino group.
 7. Thediamine of claim 1 where R'' is p,p'' diphenylene ether and R2 isphenyl.
 8. The diamine of claim 1, which is2-diphenylamino-4,6-bis(3''-aminoanilino)-s-triazine
 9. The diamine ofclaim 1, which is 2-diphenylamino-4,6-bis(4''-aminoanilino)-s-triazine.10. The diamine of claim 1, which is2-diphenylamino-4,6-bis(2''-aminoanilino)-s-triazine.
 11. The diamine ofclaim 1, which is 2,4-bis(3''-aminoanilino)-s-triazine.
 12. The diamineof claim 1, which is2-dimethylamino-4,6-bis(3''-aminoanilino)-s-triazine.
 13. The diamine ofclaim 1, which is 2-amino-4,6-bis(3''-aminoanilino)-s-triazine.
 14. Thediamine of claim 1, which is2-phenyl-4,6-bis(3''-aminoanilino)-s-triazine.
 15. The diamine of claim1, which is2-diphenylamino-4,6-bis(4''-(4''''-aminophenoxy)anilino)-s-triazine. 16.The diamine of claim 1, which is2-diphenylamino-4,6-bis(4''-(4''''-aminobenzyl)anilino)-s-triazine. 17.A diamine-dioxane complex wherein said diamine has the formula
 18. Thecomplex of claim 16 wherein the ratio of the diamine to dioxane is 1:1.19. The complex of claim 16 wherein the ratio of the diamine to dioxaneis 1:0.75.